A temperature-induced reversible transformation between paratacamite and herbertsmithite

The crystal chemistry of paratacamite has been re-evaluated by studying a crystal from the holotype specimen BM86958 of composition Cu_3.71Zn_0.29(OH)₆Cl₂ using single-crystal X-ray diffraction at 100, 200, 300, 353, 393 and 423 K. At 300 K paratacamite has space group $Rbar{3}$ with unit-cell parameters a 13.644 and c 14.035 Å and exhibits a pronounced subcell, a′ = ½a and c′ = c, analogous to that of the closely related mineral herbertsmithite, Cu₃Zn(OH)₆Cl₂. Between 353 and 393 K, paratacamite undergoes a reversible phase transformation to the herbertsmithite-like substructure, space group $Rbar{3}m$ , unit-cell parameters a 6.839 and c 14.072 Å (393 K). The transformation is characterised by a gradual reduction in intensity of superlattice reflections, which are absent at 393 and 443 K. On cooling from 443 to 300 K at ~10 K min^?1, the superlattice reflections reappear and the refined structures ( $Rbar{3}$ ) of the initial and recovered 300 K states are almost identical. The complete reversibility of the transformation establishes that paratacamite of composition Cu_3.71Zn_0.29(OH)₆Cl₂ is thermodynamically stable at ambient temperatures. The nature of the rhombic distortion of the M(2)O₆ octahedron is discussed by considering two possibilities that are dependent upon the nature of cation substitution in the interlayer sites.